Organo(halo) disulfur tin derivatives and the process of preparing the same

ABSTRACT

This invention comprises novel compounds exhibiting one direct carbon to tin bond, one direct halogen to tin bond and two direct sulfur to tin bonds, methods of preparing these novel compounds, and to polymers stabilized by these novel compounds against the deteriorative effects of heat and light.

United States Patent Wowk [451 May 23, 1972 [54] ORGANO(HALO) DISULFURTIN DERIVATIVES AND THE PROCESS OF PREPARING THE SAME [52] US. Cl...260/429.7, 260/4575 K [5 l Int. Cl. ..C07f 7/22 [58] Field of Search..260/429.7

[56] References Cited UNITED STATES PATENTS 3,542,825 11/1970 Hoye..260/429.7

Primary Examiner-Tobias E. Levow Assistant Examiner-Wench F. W. BellamyAttorneyLewis C. Brown, Kenneth G. Wheeless and Robert P. GrindleABSTRACT This invention comprises novel compounds exhibiting one directcarbon to tin bond, one direct halogen to tin bond and two direct sulfurto tin bonds, methods of preparing these novel compounds, and topolymers stabilized by these novel compounds against the deteriorativeeifects of heat and light.

18 Claims, No Drawings ORGANOGIALO) DISULFUR TIN DERIVATIVES AND THEPROCESS OF PREPARING THE SANEE This invention relates to novel organotincompounds and to novel stabilized halogen-containing polymercompositions.

Halogen-containing polymers, including homopolymers and copolymers ofvinyl chloride and vinylidene chloride, are materials which have provenuseful, because of their desirable physical properties. Uses of thesematerials have been limited, however, by their inherent instability whenexposed to conditions of heat and light. Under such conditions, thehalogencontaining polymer may discolor, become brittle, crack, check, orotherwise suffer deterioration of its physical properties. Thus,unstabilized chlorine-containing polymer compositions may be highlyunsatisfactory for outdoor use where they may be subjected to both heatand light. Various techniques are known for stabilizing these polymersagainst degradation in the presence of heat alone or light alone but nosingle stabilizer compound has been found which confers the high degreeof both heat and light stability which is required for outdoor use.

A further defect of prior art stabilizers is that they may normally beviscous liquids or pasty gels. They may thus be considerably moredifficult to handle than solid stabilizers.

It is an object of this invention to provide novel organotin compoundswhich may be characterized by their unexpectedly superior physicalproperties. It is a further object of this invention to provide novelchlorine-containing polymer compositions characterized by their highresistance to degradation during outdoor exposure.

This invention comprises novel compounds exhibiting one direct carbon totin bond, one direct halogen to tin bond and two direct sulfur to tinbonds.

This invention also comprises halogen-containing polymers stabilizedagainst the deteriorative effects of heat and light comprising ahalogen-containing polymer and a stabilizing amount of a compoundexhibiting one direct carbon to tin bond, one direct halogen to tin bondand two direct sulfur to tin bonds.

The novel compounds of this invention include those of the formula:

wherein X is a halogen atom and R, R, and R are hydrocarbons.

The novel compounds of this invention also include those of the formula:

wherein R is a monovalent hydrocarbon radical exhibiting from one to 18carbon atoms, R is a divalent hydrocarbon radical exhibiting from one to18 carbon atoms and X is a halogen atom.

The novel compounds of this invention may be prepared by reacting acompound of the formula RSn(Ol-l X wherein R is a hydrocarbon radicalselected from the group consisting of alkyl, alkenyl, cycloalkyl,aralkyl, aryl, and alkaryl and X is halide with one or more primarymercaptans, secondary mercaptans, tertiary mercaptans, mercaptoalcohols, esters of mercapto alcohols, mercapto acids or mercapto acidesters.

The novel compounds of this invention thus include those of the formula:

In the formula R and R are hydrocarbon radicals selected from the groupconsisting of alkyl, cycloalkyl, aralkyl, alkaryl, and aryl. R may beselected from the same group as R. R may also be a residue of acarboxylic acid ester --R"COOR. In these formulae R, R (which may be thesame as each other or different) may be selected from the same group asR and R are selected from. In these formulae R and R are hydrocarbonradicals selected from the group consisting of alkyl, cycloalkyl,aralkyl, alkaryl, and aryl, and X is a halogen atom selected from thegroup consisting of chlorine, bromine and iodine. When R or R is alkyl,it may be a straight chain alkyl or a branched alkyl, including methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,n-amyl, neopentyl, isoamyl, n-hexyl, isohexyl, heptyls, octyls, decyls,dodecyls, tetradecyl, octadecyl, etc. Preferred alkyl includes alkylshaving less than about 20 carbon atoms. When R or R is cycloalkyl, itmay typically be cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.When R or R is aralkyl, it may typically be benzyl, [3-phenylethyl,y-phenylpropyl, ,B-phenylpropyl, etc. When R or R is aryl, it maytypically be phenyl, naphthyl, etc. When R or R is alkaryl, it maytypically be tolyl, xylyl, p-ethylphenyl, p-nonylphenyl, etc. R or R maybe inertly substituted, e.g., may bear a non-reactive substituent suchas alkyl, aryl, cycloalkyl, aralkyl, alkaryl, ether, etc.

Typical novel compounds of this invention include:

monobutylmonochlorotin S,S' bis(lauryl mercaptide),monobutylmonochlorotin S,S bis( octyl mercaptide),monobutylmonochlorotin S,S bis(benzyl mercaptide),monobutylmonochlorotin S,S bis(xylyl mercaptide), monobutylmonochlorotinS,S bis(cyclohexyl mercaptide), monobutylmonochlorotin S,S' bis(phenylmercaptide), monooctylmonochlorotin S,S' bis(lauryl mercaptide),monooctylmonochlorotin S,S bis(octyl mercaptide), monooctylmonochlorotinS,S bis(benzyl mercaptide), monooctylmonochlorotin S,S bis( xylylmercaptide), monooctylmonochlorotin S,S bis(cyclohexyl mercaptide),monocyclohexylmonochlorotin S,S' bis(lauryl mercaptide),monomethylmonochlorotin S,S bis(lauryl mercaptide),monomethylmonochlorotin S,S' bis(benzyl mercaptide),

monomethylmonochlorotin S,S bis(cyclohexyl mercaptide),monomethylmonochlorotin S,S' bis(xylyl di-mercaptide),monobutylmonochlorotin S,S bis(isooctyl mercaptoacetate),monooctylmonochlorotin S,S' bis(isooctyl mercaptoacetate),monocyclohexylmonochlorotin S,S' bis(isooctyl mercaptoacetate),monomethylmonochlorotin S,S' bis(isooctyl mercaptoacetate),monophenylmonochlorotin S,S bis(isooctyl mercaptoacetate),monophenylmonochlorotin S,S bis(isooctyl mercaptoacetate),monobutylmonochlorotin S,S' bis(lauryl mercaptoacetate),monobutylmonochlorotin S,S bis(benzyl mercaptoacetate),monobutylmonochlorotin S,S bis(dodecyl thioglycollate),monobutylmonochlorotin S,S, bis(isooctyl mercaptopropionate),monooctylmonochlorotin S,S bis(isooctyl mercaptopropionate),monocyclohexylmonochlorotin S,S bis(isooctyl mercaptopropionate),monoethylmonochlorotin S,S bis(isooctyl mercaptopropionate),monophenylmonochlorotin S,S bis(isooctyl mercaptopropionate),monobutylmonochlorotin S,S bis(lauryl mercaptopropionate),monobutylmonochlorotin S,S bis(benzyl mercaptopropionate),monobutylmonochlorotin S,S' bis(isooctyl mercaptopropionate), andmonobutylmonochlorotin S,S bis( dodecyl mercaptopropionate).

The reactant RSn(OH) X of this invention is prepared from the compoundRSnX Typical compounds RSnX include the following: ethyltin trichloride,propyltin trichloride, n-butyltin trichloride, hexyltin trichloride,octyltin trichloride, phenyltin trichloride, o-tolyltin trichloride,benzyltin trichloride, butenyltin trichloride, ethynyltin trichloride,butyltin tribromide, and n-octyltin tribromide.

Compounds such as butyltin bromide dichloride may be employed.Preferably the compound RSnX is a chloride and the preferred compoundsmay be n-butyltin trichloride and n-octyltin trichloride. The processfor preparing the compound RSn(Ol-l) X includes maintaining an aqueousreaction mixture containing RSnX adding to said reaction mixture acatalytic amount of a catalyst selected from the group consisting ofaluminum chloride, titanium tetrachloride, bismuth trichloride, ferricchloride, cobalt chloride, nickel chloride, cadmium chloride, zirconiumtetrachloride, boron trifluoride etherate, mercuric chloride, cupricchloride, trifluoracetic acid, and zinc fluoride; thereby forming aprecipitate containing RSn(Ol-l) X-, and recovering said precipitatefrom said aqueous reaction mixture. In practice, 10-200 parts, say 17.5parts of RSnX are added to 100 parts of aqueous reaction medium,preferably water. Catalyst, preferably aluminum chloride, is added in anamount of 0. l-] parts, say 0.95 parts, and the solution allowed tostand for up to 2-3 hours. The solid precipitate which forms may beseparated as by filtration and washed with l0-l000 parts, say 15 partsof water. After further washing with 6-60 parts, say 12 parts of, e.g.,acetone, the precipitate may be air-dried. The product, typicallyobtained in an amount of 2.5 parts, is recovered from the filtrate.

The process for conducting the reaction includes maintaining an aqueousreaction mixture containing RSnX adding to said aqueous reaction mixturebase in an amount not stoichiometrically greater than the amount of RSnXthereby forming a precipitate containing RSn(OH) X; and recovering saidprecipitate from said aqueous reaction mixture. In practice, 10-100parts, say 20 parts of RSnX may be added to 100 parts of aqueousreaction medium, preferably water. Base, preferably an alkali metalhydroxide such as potassium hydroxide, sodium hydroxide may be addedthereto preferably as a solution containing l-50 parts, say 10 parts ofbase in 100 parts of water. The amount of base added should not bestoichiometrically greater than, and preferably equal to, the amount ofRSnX i.e., two equivalents of base per mole of RSnX The productRSn(Ol-l) X may precipitate and, preferably after standing for 4-12hours be separated as by filtration. The precipitate may be washed with50-500 parts, say 200 parts of water (which has been acidifiedpreferably with hydrochloric acid) to pH of preferably about 2.0. Theproduct may then be dried.

The process for preparing RSn(Ol-l) X when R is alkyl may includemaintaining an aqueous reaction mixture containing RSnX heating saidreaction mixture thereby forming a precipitate containing RSn(OH) Xproduct; and recovering said precipitate from said aqueous reactionmedium. In practice, l-40 parts, say four parts of RSnX may be added to100 parts of aqueous reaction medium preferably water. The reactionmixture may then be heated to 70120 C, preferably to reflux temperaturefor l-5 hours, preferably 2 hours. The product RSn(OH) X may copiouslyprecipitate and be recovered by filtration. The precipitate may bewashed with 2-10 parts, say five parts of water (which preferably hasbeen acidified preferably with hydrochloric acid to pH of preferably2.4). The product may be further washed with acetone (acidified to pH of2.4) and air-dried.

Typical reactants RSn(0H X include the following: ethyltin chloridedihydroxide, propyltin chloride dihydroxide, nbutyltin chloridedihydroxide, iso-butyltin chloride dihydroxide, hexyltin chloridedihydroxide, octyltin chloride dihydroxide, phenyltin chloridedihydroxide, o-tolyltin chloride dihydroxide, benzyltin chloridedihydroxide, butenyltin chloride dihydroxide, and ethynyltin chloridedihydroxide.

A reaction mechanism for the formation of the novel compounds of thisinvention is clearly illustrated by the following equations:

These equations graphically show that a reaction occurs between themercapto radical and the compound RSn(OH) X whereby water splits oh anda chemical bond is formed between the tin and sulfur. These equationsfurther illustrate the necessity of two molecules of the mercaptocompound per mole of the compound RSn(0H) X to obtain the desiredreaction and the desired novel compound having a 2: 1 ratio of sulfur totin.

It is within the scope of this invention that pure, impure or commercialgrades of the reactants may be employed satisfactorily. in general, purecompounds of the above formulae may be prepared from pure raw materials.However, these novel compounds may be diluted with innocuous, inertmaterials thereby permitting the use of technical grades of materials orintermediates in their preparation.

Any suitable reaction temperatures may be employed. It is ordinarilypreferred to use room or slightly elevated temperatures of the order upto about C. The exothermic nature of the reaction between the compoundRSn(OH) X and the sulfur containing compounds affords a considerablesaving in the expenditure of external heat. The presence of waterproduced by the condensation reaction usually requires an additionalheating or refluxing in order to strip said water from the reactionproduct, though it may be removed in any suitable matter.

The use of inert organic solvents as a medium for a reaction such astoluene, benzene, methyl alcohol, etc., is contemplated. The presence ofsuch solvent facilitates the desired reaction. The solvent may beeliminated from the reaction product at the completion of the reactionby any suitable means. This may be accomplished by vaporizing thesolvent under vacuum at elevated temperatures. Pressures of about 2 to30 mm of mercury at temperatures of 75 to C are satisfactory inaffecting the removal of toluene or like solvent from the reactionproduct.

By these procedures, the novel compounds of this invention can beobtained in almost theoretical yields. These yields are indicative thatit is not necessary to use an excess of either reactant, the totalamount of starting materials being substantially utilized in theformation of the final reaction product.

Polymers or resins which may be stabilized by practice of this inventionare halogen-containing organic polymers typically those which containchlorine atoms bonded to the polymer chain. These polymers includepolyvinyl chloridetype polymers, e.g., polyvinyl chloride,polyvinylidene chloride, etc. They may also include copolymers formed bythe copolymerization of vinyl chloride or vinylidene chloride with eachother or with other ethylenically unsaturated monomers. Ethylenicallyunsaturated monomers may be compounds which contain polymerizablecarbon-to-carbon double bonds and may include acrylates such as acrylicacid, ethyl acrylate, acrylonitrile, etc.; vinyl monomers such asstyrene, vinyl acetate, etc.; maleates such as maleic acid, maleicanhydride, maleate esters, etc.

The polymers may be either rigid or flexible. When Rigid polymers areemployed, they may include impact modifiers, pigments and/or fillers,lubricants, etc., in addition to the resin and stabilizer. When flexiblepolymers are employed, they may include plasticizer (primary andsecondary), pigments and/or fillers, lubricants, etc., in addition tothe resin and stabilizer.

In general the synthetic resins which can be stabilized according tothis invention include the following polymers which may or may not bemixed with other stabilizers, additives, flameproofing agents, dyes,pigments, etc.:

a. l-lomopolymer of vinyl chloride,

b. Homopolymer of vinylidene chloride,

c. Copolymers of vinyl chloride and acrylonitrile,

d. Copolymers of vinylidene chloride and acrylonitrile,

e. Copolymers of vinylidene chloride, acrylonitrile and N-isopropylacrylamide,

f. Copolymers of vinyl chloride and vinyl acetate,

g. Copolymers of vinyl chloride, acrylonitrile, and N-butyrylacrylamide,

h. Copolymers of vinyl chloride, methyl methacrylate and vinyl acetate,

i. Copolymers of vinyl chloride or vinylidene chloride withacrylonitrile and N-vinylpyridine,

j. Copolymers of vinyl chloride or vinylidene chloride withacrylonitrile mixed with a homopolymer of an N-alkylacrylamide e.g.,N-iso-propylacrylamide, N-octylacrylamide, etc.

k. Copolymers of vinyl chloride or vinylidene chloride with acrylontrilemixed with a homopolymer or copolymer of a-vinylpyrrolidone,

1. Copolymers of vinyl chloride or vinylidene copolymers of anN-alkylacrylamide and acrylonitrile,

in. Other copolymers and mixtures of homopolymers or copolymers of vinylchloride and/or vinylidene chloride with or without othermonoolefinically unsaturated polymerizable monomers containing from twoto 20 or more carbon atoms, especially those containing from two toeight carbon atoms and no more than one nitrogen atom and no more thantwo oxygen atoms.

The methods for preparing the synthetic resins described above are wellknown and such methods and a great variety of such synthetic resins aredescribed in the prior art. These synthetic resins are useful inpreparing fibers, films, molding compositions, coating materials,wrapping materials, electrical insulation, fabrics, rope, plastic, pipe,paints, laminating materials for safety glass, adhesives, etc. Syntheticresins as stabilized in accordance with this invention are especiallyadvantageous in synthetic fibers and products made therefrom such asrugs, wearing apparel, draperies, seat covers, upholstery, rope,cigarettes filters, etc. Resistance to weathering e.g., moisture andultraviolet light) is especially important for items exposed to out ofdoors conditions. Resistance to ultraviolet light is also important forrugs, draperies, automobile seat covers, porch furniture upholstery andthe like which may receive considerable sunlight.

The following examples are for illustration and are not to be construedas limiting the scope of the invention.

EXAMPLE 1 Elemental Percentage of Calculated Found EXAMPLE 2 Preparationof monobutylmonochlorotin S,S bis(isooctyl mercaptoacetate)Monobutylmonochlorotin S,S' bis(isooctyl mercaptoacetate) was preparedby adding 24.6 grams (0.10 moles) of butylchlorotin dihydroxide and 40.9grams (0.20 moles) of isooctyl mercaptoacetate to 150 milliliters ofbenzene in a 300 milliliter reaction flask equipped with a stirrer, athermometer, and a reflux condenser. The foregoing mixture was heated,refluxed for ninety minutes, and stripped of the benzene solvent. Theresulting yellow purified product exhibited a weight of 57.3 grams andwas analyzed as containing the following:

Elemental Percentage of Calculated Found Cl/Sn Atomic Ratio 1.00 0.96

EXAMPLE 3 Preparation of monobutylmonochlorotin S,S bis(laurylmercaptide) Monobutylmonochlorotin S,S' bis(lauryl mercaptide) wasprepared by adding 46.4 grams (0.20 moles) of lauryl mercaptan and 24.6grams (0.10 moles) of butylchlorotin dihydroxide to 130 milliliters ofbenzene in a 500-milliliter flask equipped with a stirrer, thermometer,and reflux condenser. The aforementioned mixture was refluxed for 2hours at a temperature of C. The benzene solvent was vacuum stripped andthe product thus obtained was clarified by filtration. The productexhibited a weight of 66.9 grams, a 99.4 percent yield, and uponanalysis the following characteristics:

Elemental Percentage of Calculated Found Cl/Sn Atomic Ratio 1.00 0.92

EXAMPLE 4 Preparation of monobutylmonochlorotin S,S bis(octadecylmercaptoacetate) Monobutylmonochlorotin S,S bis(octadecylmercaptoacetate) was prepared by adding 59.9 grams (0.163 moles) ofoctadecyl thioglycollate and 20.0 grams (0.0817 moles) ofbutyl-chlorotin dihydroxide to 200 milliliters of toluene. The processwas conducted as was that of Example 1. The purified product exhibited aweight of 67.6 grams, a 93 percent yield, and as an elemental analysis,the following:

Elemental Percentage of Calculated Found Sn 12.43 1 2.68 S 6.7 6.50 CI3.71 3.86

EXAMPLE 5 Elemental Percentage of Calculated Found Sn 20.8 20.86 S(metal bonded) 1 1.25 10.83 CI 6.2 5.29

EXAMPLE 6 Preparation of monobutylmonochlorotin S,S' bis(dodecylthioglycollate) The novel compound monobutylmonochlorotin S,Sbis(dodecyl thioglycollate) was prepared by adding 54.1 grams (0.204moles) of dodecyl thioglycollate and 25.0 grams (0.102 moles) ofbutyltin dihydroxide to 200 milliliters of toluene. The process ofExample 1 was followed in obtaining a product exhibiting a weight of69.6 grams, a yield of 99 percent of theoretical and upon elementalanalysis the following:

Elemental Percentage of Calculated Found EXAMPLE 7 Elemental Percentageof Calculated Found Sn 16.9 16.53 S 9.1 3 8.71 Cl 5 .05 4.61

EXAMPLE 8 Preparation of monobutylmonochlorotin S,S'-p-xylylene a,a-dimercaptide Monobutylmonochlorotin S,S'-p-xylylene a, a'-dimercaptidewas prepared by adding 25.0 grams (0.102 moles) of butylchlorotindihydroxide and 17.7 grams (0.102 moles) of pxylylene a, a'-dimercaptideto 1 liter of toluene contained in a reaction vessel equipped with astirrer, a thermometer, and a reflux condenser. The foregoing mixturewas heated with agitation to form an azeotrope at 100 C. The toluenesolvent was vacuum stripped and impurities were separated from theproduct by filtration. The purified product exhibited a weight of 34.8grams and a yield of 90 percent. Analysis of the product indicated thefollowing:

Elemental Percentage of Calculated Found Sn 3 1.27 30.27 S 16.90 16.70Cl 9 .34 8.29

The novel heat and light stable compositions of this invention may beformulated by such techniques as milling, dry blending, Banburyblending, or any other commonly employed formulating techniques.Whatever formulating technique be employed, it will be desirable tosubstantially complete and unifomily disperse the novel stabilizingcompound throughout the vinyl chloride polymer composition.

It is a feature of the novel stabilizer systems of this invention thatit permits attainment of stabilized halogen-containing polymers andresins, particularly vinyl halide polymers such as vinyl chloridecharacterized by their resistance to the deteriorative effect of heat.The degrees of stabilization attained in such systems may beconsiderably in excess of that previously attainable by any prior artstabilizer system.

Because of the outstanding properties of this novel stabilizer system,it is possible to effect stabilization with lower quantities and therebyto obtain a more effective system on a costperformance basis.

To illustrate the unexpected and outstanding results which may beattained by practice of this invention, the following Examples 9, l0,and l l are set forth wherein all parts are parts by weight unlessotherwise indicated.

In Examples 9, l0, and ll, the rigid vinyl chloride polymer employed wasthat having a specific gravity of 1.40, a Shore Durometer D hardness ofand an ultimate tensile strength of about 7,000 psi, sold under thetrademark Diamond 450.

The selected compositions were thoroughly blended by placing thepolyvinyl chloride on a two-roller differential mill which wasoil-heated to a temperature of 175 C together with the noted quantity offirst and second stabilizers, and the mixture was milled for about 5minutes. A continuous band of the composition formed around one of therollers. This band was cut and the composition was removed from the hotroller as a continuous sheet. Squares of this material measuring 2.54 X2.54 cm were cut for heat stability testing.

For the heat stability test, the squares were placed in an air ovenregulated to maintain a temperature of 205 C. Samples of eachcomposition were removed from the oven at 15- minute intervals and wererated visually as to color change and degradation according to thefollowing scale:

7 clear, water-white 6 off-white 5 slightest degree of yellowing 4definite yellow color 3 deep yellow-brown color 2 deep brown color 1dark brown to black color The length of time in minutes required toreach a value of 3 or less was recorded as the Heat Stability Value.

In Example 9 as hereinafter set forth, parts of the vinyl chloridepolymer was tested with the addition of 2 parts of the compound ofExample l, monobutylmonochlorotin S,S bis(isooctyl rnercaptopropionate).in Example 10, the novel compound of Example 2, monobutylmonochlorotinS,S bis(isooctyl mercaptoacetate) was added in amount of 2.0 parts andno other stabilizer was present. In Example 1 l, the stabilizer was thenovel compound of Example 3, monobutylmonochlorotin S,S bis(laurylmercaptide), present in amount of 2.0 parts and no other stabilizer waspresent.

The results of the heat stability tests are presented in Table I asfollows:

TABLE I Heat Stability Value From Table I, it will be apparent that thecompositions prepared in accordance with this invention are superior,having a Heat Stability Value of 40 minutes and a Color After Milling of7. The experimental Examples 9, l0, and 11 show stabilization bycompositions particularly characterized by low cost, low sulfur content,and substantially lower odor during milling.

It is clear from Examples 9, l0, and l 1 that the Heat Stability Valueof the novel product of this invention is outstanding. Furthermore, theColor After Milling of the novel product is very high, being ratednumerically as 7, which is outstandingly superior.

Although this invention has been illustrated by reference to specificexamples, the scope of this invention is limited solely by the scope ofthe appended claims.

I claim:

1. The process for preparing compounds exhibiting one direct carbon totin bond, one direct halogen to tin bond and two direct sulfur to tinbonds which comprises reacting a compound RSn(Ol-l) X wherein R is ahydrocarbon and X is halogen with a sulfur containing compound of aformula selected from the group consisting of R'(Sl-l),, and HSR"COORwherein R is a hydrocarbon radical having a valence of y, R" is adivalent hydrocarbon radical, R is a monovalent hydrocarbon radical andy is the integer l or 2 and recovering said novel compound.

2. The process of claim 1 wherein said sulfur containing compound of theformula R(SH),, is an alkyl mercaptan of from one to carbon atoms and yis l.

3. The process of claim 1 wherein said sulfur containing compound is adimercaptan HSRSH wherein R is a hydrocarbon.

4. The process of claim 3 wherein R is aralkylene 5. The process ofclaim 3 wherein R is alkylene.

6. The process of claim 1 wherein R is alkyl 7. The process of claim 1wherein X is a chloride.

8. The process for preparing compounds exhibiting one direct carbon totin bond, one direct halogen to tin bond and two direct sulfur to tinbonds which comprises maintaining an aqueous reaction mixture containingRSnX adding to said aqueous reaction mixture a base in amount notstoichiometrically greater than the amount of RSnX thereby forming aprecipitate containing RSn(OH) X; recovering said precipitate from saidaqueous reaction mixture, adding to said RSn(OH) X, thus recovered, asulfur containing organic compound of a formula selected from the groupconsisting of R'(SH),, and HSR"COOR wherein R is a hydrocarbon radicalhaving a valence of y, R is a divalent hydrocarbon radical, R is amonovalent hydrocarbon radical and y is the integer l or 2 therebyforming said novel compound and recovering said novel compound.

9. The process of claim 8 wherein said sulfur containing compound is ofthe formula RSl-l wherein R is a hydrocarbon.

10. The process of claim 8 wherein said sulfur containing compound is anester of a sulfur containing organic acid.

1 l. The compound which has the formula:

16. The compound of claim 11 wherein X is chloride. 17. A compound insubstantially pure form selected from those of the general formula Sn SCHIC) wherein R represents an isooctyl, octadecyl, cyclohexyl, ordodecyl radical.

18. A compound in substantially pure form selected from those of thegeneral formula Sn S CHQCHzCk C1 OR 2 wherein R represents a butyl or ann-octyl radical and R represents an isooctyl radical.

2. The process of claim 1 wherein said sulfur containing compound of theformula R''(SH)y is an alkyl mercaptan of from one to 20 carbon atomsand y is
 1. 3. The process of claim 1 wherein said sulfur containingcompound is a dimercaptan HSR''SH wherein R'' is a hydrocarbon.
 4. Theprocess of claim 3 wherein R'' is aralkylene
 5. The process of claim 3wherein R'' is alkylene.
 6. The process of claim 1 wherein R is alkyl 7.The process of claim 1 wherein X is a chloride.
 8. The process forpreparing compounds exhibiting one direct carbon to tin bond, one directhalogen to tin bond and two direct sulfur to tin bonds which comprisesmaintaining an aqueous reaction mixture containing RSnX3; adding to saidaqueous reaction mixture a base in amount not stoichiometrically greaterthan the amount of RSnX3 thereby forming a precipitate containingRSn(OH)2X; recovering said precipitate from said aqueous reactionmixture, adding to said RSn(OH)2X, thus recovered, a sulfur containingorganic compound of a formula selected from the group consisting ofR''(SH)y and HSR''''COOR'''''' wherein R'' is a hydrocarbon radicalhaving a valence of y, R'''' is a divalent hydrocarbon radical, R''''''is a monovalent hydrocarbon radical and y is the integer 1 or 2 therebyforming said novel compound and recovering said novel compound.
 9. Theprocess of claim 8 wherein said sulfur containing compound is of theformula RSH wherein R is a hydrocarbon.
 10. The process of claim 8wherein said sulfur containing compound is an ester of a sulfurcontaining organic acid.
 11. The compound which has the formula: whereinR is a monovalent hydrocarbon radical exhibiting from one to 18 carbonatoms, R'' is a divalent hydrocarbon radical exhibiting from one to 18carbon atoms and X is a halogen atom.
 12. The compound of claim 11wherein R is alkyl.
 13. The compound of claim 11 wherein R'' isaralkylene.
 14. The compound of claim 11 which is monobutylmonochlorotinS, S''-p-xylyl- Alpha , Alpha ''-dimercaptide.
 15. The compound of claim11 wherein R is alkyl and R'' is alkylene.
 16. The compound of claim 11wherein X is chloride.
 17. A compound in substantially pure formselected from those of the general formula wherein R represents anisooctyl, octadecyl, cyclohexyl, or dodecyl radical.
 18. A compound insubstantially pure form selected from those of the general formulawherein R represents a butyl or an n-octyl radical and R'' represents anisooctyl radical.